Resin and process of producing the same



a Grantwood, in the county mama Apr. 8, 1924.

. UNITED STA ES PATENT OFFICE.

CRAB-LIB B. DOWNS, OF CLII'FSIDE, LOUIS WEISBIBG, .Ol' GRANTWOOD, NEWJERSEY, ASSIGNOBS TO 'IHE BABBETT COHPANY, A CORPORATION OF NEW JER-SEY.

. .RESIN AND PROCESS OF PRODUCING THE am.

No Drawing. Original application died December 28, 1920, Serial Io.432,408 Divided and this applicatlon fled September 8d, 1921. Serial Ho.608,982.

' To all whom it may concern:

Be it known that we, CHARLES R. Downs 1 and Louis VI-IISBERG, citizensof the United States, residing at (1) Cliflside and 22) of (1) and 2)Bergen and State of (1) and (2) New Jersey, have invented certain newand ful Improvements in Resins andProcesses of Producing the Same, ofwhich the following to is a specification. p

This is a division of our application,

Serial No. 432,408, filed December 22, 1920. Resinous materials ofwidely different properties have heretofore been made from it! g1 with adibasic aromatic acid alone, a dibasic cerol by suitable combinationthereof aliphatic acid alone and also with a mix- ,t re of varyingproportions of both an aromatic dibasic and an aliphatic dibasic macid.See U. S'. Patents: 1,082,106, Dec.

1 23, 1919 1,091,627, Mar. 91,1914; 1,091,928,;

Mar. 31, 1914; 1.091, 732, Mar. 31, 1914; 1,098,728, June 2, 1914;1,098,776, June 2, 1914; 1,098,777, June 2, 1914; 1,108,829,

Aug. 25, 1,108,331, Aug. 25, 1914;-1,10s,332, Aug. 25, 1914; 1,119,592,Dec. -1, 1914.

' In the case of those materials from lycerol an phthalic acid-(ananhydride-orming aromatic dibasic acid) alone this mmbination has beenobserved to pass through three stages, a first solid st the A- stage), asecond solid stage (t ed stage) anda third solid stage (theC-stag'e). heultimate industrial utility of these resinous roducts lies in their usein'molding and like com )ositions. For this the above-described iI-stageproduct isvery superior to the-corresponding B-stage product and. can

cases where the B-stage product isuseless.

In the case of those materials from glycerol and-a dibasic aliphaticacid or a mixture of dibasic aliphatic acid and an anhy-f dridc-t'ormingdibasic aromatic acid, a solid product other than that corresponding tothe B-stage product of the glycerol-aromatic dibasic acid group hasnever been described or indicated, although such B-stage products "he vcthcn'iselves been known for many years. 1 -.\"o\v, it. remained-for usto discover that these relatively useless B-s'tage products can beconverted into very useful and-highly de- "sirahle' products which arethen among the 1914;'1,10s,3a0, Aug. 25, 1914;.

-be used successfully in a large number of from glycerol and apolynuclear aromatic acid, such as diphenic acid, 1.8 na hthalic acid,benzoyl benzoic acid, methylenz oylbenzoic acid andchlor-benzoyl-benzoic acid, and an ali hatic dibasic acid. Furthermore,we have so discovered that a tribasic aliphatic acid, such as citricacid and malo malic acid, can be employed in place of dibasic aliphaticacids in roducing useful C- stage', roducts either a one or in mixturewith t e above-named aromatic acids. I, In converting these relativelyuseless B- stage. roducts into our new products, we have t ereb causedthe latter to retain substantially l of the elasticity and flexibilityof the B-stage products from which they are respectively same timeincreased the electrical insulating properties of our new productsbeyond that of the corresponding B- stage products. These changes, aloneor together, would not add to the utilityfof the B-stage products in anysubstantial manner. However, ournew products do differ from the B-stageproducts from which they are respective y derived in one most essentialparticular and the.

all decomposed or so altered by water that they cannot be employed inplaces where water contact is unavoidable such as in submarine cables orin exterior and openly exposed positions where they are subject toaction of dew, rain, snow or frost. The B- stag'e products under" theseconditions become soft or spongy or porous, lose in elasticityandflexiblity and also lose in cohesiveness, resistance toshock, frictionand to the passage of electric current, while our new products suffer nomaterial change in any or all of these respects through such watercontact, while at the same time they can flilllfllly well be employed inany and all 0t er uses to which these B-stage products have beensuccessfully put.

To effect this change of the old B-stage made, while we have at theproducts above referred to into our new products, we apply prolorged andhigh heating to these -stage pr ucts until the change to our newproducts has been satisfactorily effected. In general, thisiis the samemeans employed to convert the B- stage products of the glycerolhthalicacid resin into the corresponding -stage product. (See U. S. Patent1,108,330, August 25, 1914.)

In general, these A-sta 0 products we operate with are hard wit outbeing sticky and are fusible; upon proper heating these A-stage productsall become infusi cle and reach the B-stage which B-stage, whensubmerged in boiling distilled water, becomes coated with a bloom,always in less than two minutes; these B-stage products when furtherproperly heat-ed remain infusible but lose the above describedSBI'iSltlVGIN-BSS to water when the C-stage has been reached. Theseproperties are so sharp and so characteristic that an operator can, withcertainty, determine when he has arrived at each of these three stages,when making these materials in bulk.

\Ve have employed the following polybasic aliphatic acids; among thedibasic acids we have employed and found useful are the following:fumaric acid; maleic acid; malic acid; succinic acid and tartaric acid;among the tribasic acids we have em ployed and found useful are citricacid and male malic acid.

We have employed the following mixtures of the foregoing as well asothers not mentioned below. The figures in the table represent themolecular proportions of each acid used.

\Ve have emplo 'ed phthalic acid, an aromatic dibasis acid, both assuch, and as its anhydride, in mixture with the foregoing dibasicalipathic acids, as shown, for example, in the following table:

NO Phthalic Fumaric Maleic Malic Succinlc Tartaric acid. acid. acid.acid. acid. acid.

We have employed glycerol, glycol, diglycerol and triglycerol, all ofwhich are olyhydric alcohols or polyhydric alcoholic odies. We make noclaim to a resin inade from phthalic anhydridc alone because this is thesubject of U. S. Patent No, iioaaao of August 25, 191-}. We havediscovered, however, that diphenic acid, 1.8 naphthalic acid and thebenzoyl-benzouic acids form with the above-mentioned alcohols resinswhich are unaffected by water and we here- ;in claim these resins aspart of our invention. ()t' the various bei zoyhlieuzoic acids we haveused bcnzoyl-benzoic acid, methylbenzoyl-benzoic acid andchlor-benzoyl-benzoic acid. which we made by condensation of phthalicanhydride with beuzol, toluol and chlor-benxol respectively in thepresence of aluminum chloride. in the manner well known to chemists andhave obtained satisfactory resins.

\Ve have also made resins with each of these aromatic acids mixed withone or more of the previously mentioned olybasic aliphatic acids andhave obtaine satisfactory and useful results.

PRODUCING THERE PRODUCTS IN BULK.

E trample I-Pm*t A.

-lsic m resin from iylyccrol 11ml mu/cic tuzzrl.-Heat together quantitieof glycerol and maleic acid in the pro ortion of one molecular weight ofglyceri'il to one l'l1()l0.C-- ular weight of acid. The acid dissolves,forming a homogenous mass. As the heat-- ing is continued, the meltingpoint gradually rises, and the material, which at first is quite stickyand viscous, eventually loses its stickiness and becomes more solid whencold. The completion of the first reaction can be ascertained by takingout. a small sample, and allowing it to cool. If the cooled product isviscous or tenacious but not sticky, the reaction has gone far enough.At this stage the product is soluble in acetone, making a clear solutionuseful as a varnish. By this time the melting point is usually over 90C. and may be as high as 120 C. (melting points taken by the methoddescribed on page 821, vol. 10, Journal of Industrial and EngineeringChemistry). The time required to reach this point may vary according tothe temperature at which the heating is conducted, the bulk of thematerial employed, and the rate of stirring. It is seldom advantageousto let this temperature exceed 200 C., as it is then difiicult tocontrol the next step in the reaction. On the other hand, it isdesirable to keep the temperature as high as possible (i. e., as near200 C. as possible) because the reaction otherwise proceeds slowly. Forexample, a batch of two pounds may be converted at 170 C. in ap- 1 ,mnu

. proximately 20 hours. If the material is cooled before the next stageof the reaction sets in, the product obtained is fusible and soluble incold acetone. This resin is also soluble at room temperature in ethylalcohol and ethyl acetate although not so much as in acetone. Itdissolves slightly in benzene. Cold water acts on it rapidly, causing itto become discolored and soft.

Ewample I-Part B.

-B-stage resin from glycerol and malez'c acid.He at the product of Examlo I- part A until a specimen on suita 1e test shows that it is nolonger fusible, that it is insoluble in cold acetone, and also that itis affected when submerged in boiling distilled water for two minutes.The temper-- ature of heating may be as high as in part A, but in thatcase the reaction becomes violent, frothing and evolution of heat takeplace, and the material becomes filled with ubbles. This froth productmay be rendered homogeneous y comminuting it and then molding it underheat and pressure. A buble-free product may be obtained directly,however, by heating at a temperature properly at or near the meltingpoint of the A-stage resin; the maximum temi ll ' be converted at 135C.in about ten hours from the A-stage resin to the B-stage resin.

Example IPa 1't 0'. i

O-sta e resin from glice'rol and malez'c acid. eat the productrom'Exaxnple 1- part B to a temperature of 170-200 C. until a testspecimen when submerged for two minutes in boiling distilled water doesnot show a bloom on its surface. The time required to accomplish thischange depends on the temperature used and on the bulk of the materialheated. With a large bulk "of resin it is important at first not toraise the temperature too rapidly, for the resin is not a good conductorof heat and considerable time is required to equalize the temperature.The final temperature may be as high as 250 C. when time is important.For example, a batch of two pounds may be converted at 170 C. inapproximately 30 hours. 1

In place of maleic acid of Example I,

as it is often more convenient to com we have used the following-malicacid; fumaric acid; succinic acid, and malo malic acid, and withsatisfactory results. Moreover, we have used various mixtures of theseacids as well as mixtures containin one or more of these acids togetherwith phthalic acid.

, These final C-stage products are insoluble at room temperature in thefollowing solventszacetone, ethyl alcohol, benzene, ethyl acetate,chloroform, tur ntine, ether, linseed oil, China wood oil, and petroleumtransformer oil. They are infusible but soften sufiiciently attemperatures above 140 C. to be molded under pressure. Mechanically,electrically, and chemically, these new products are superior to the Aand B- sta'ge products from which they are derived. Thus they are hard,tough,elastie, and well suited to the ordinary machining operations.They are resistant to'heat, although they burn when put in a flame. Theinsulating value of the G-stage resins is considerably higher than thatof the respective B-stgge resins from which theyare derived.

new products, moreover, are resistant to cold and to boiling water.Prolon ed contact with cold water does not diminis the lustre or polishof the surface, and the water. re mains neutral to litmus. They aresubstantially unattacked at room temperature by 20% solutions ofsulphuric, hydrochloric, nitric, or acetic acid, but they Wlll notwithstand concentrated sulphuric acid or hot concentrated nitric acid..They are not materially attacked within one hour by a 20% solution ofcaustic soda at the o dinary room temperature. p However, on boiling incontact with this solution, the resins are decomposed, forming alcoholsand sodium salts corresponding or related to the alcohols and acids usedin their manufacture.

While these new 'C-resins can be used as such for certain purposes, thebest, most convenient and practical method of manufacture is to applythe final heat treatment at the place or in the form of their ultimateuse. This is particularly the case when fillers are to be incorporatedwith the resin, und the resin and fillers before the line heat treatmentis applied.

For example, the finished C-resin ma be finely ground, mixed with asuitable ller if desired, and molded by the application of heat andpressure in the way usual in such operations. We have found that we canem loy not only the more expensive kinds 0 fillers, such as fibrousasbestos, cotton, wood pulp and the like, which have some mechanicalstren h of their own, but also the cheaper nonbrous fillers, such astalc, rotten stone, wood 'flour, ground asbestos and other like inertpowdeiymaterials having no special mechanical strength of their own,

Emample I I ture. The relative proportions of resin and filler willnaturally vary according to the particular purpose for which the moldingcom osition is intended. The mixture thus pro uced may be molded underheat and pressure, and the final heat treatment as in Example Ipart C,then ap lied with the molded object still in the mo (1, or the heattreatment may be applied first and the composition then molded. It isnot always necessary to carry out the entire heat treatment in the mold,and the molded object may be removed as soon as it has attainedsuflicient rigidity to maintain its proper form under further heating,thus releasing the mold for further use and consequently cheapening theprocess.

Ewample I II Producing a molded article containin O-resz'n from theB-resin-The B-resin 1S finely ground and allowed to stand in contactwith acetone for a considerable time. The powdered resin swells and forma jellylike mass, which. is also a suitable form for compounding with alarge proportion of filler by kneading or passing between rolls in theusual way in such operations. The composition thus produced is heated todrive off any excess of solvent and may then be handled as in thepreceding example. Alternatively, the composition may be molded beforedriving off the solvent, and the solvent may then be driven off whilethe object is still in the mold.

Example IV.

Producing a molded article containing 0- resin from the A-resz'n.TheA-resin is melted and the finely ground filler added molding operationis carried out, but the heat treatment may be interru ted at such astage that the heat applied in the snbse quent molding operationsufiices to produce a finished C-stage product.

Our new products can be distinguished with certainty from all otherheretofore known products by making the following two tests:,.

I. Place a specimen thereof in boiling distilled water; if its surfaceremains bright and does not become dull in two minutes, it iswater-resistant in the sense we have herein used and will hereafter usethat expression.

II. Boil a s imen, say 1 gram, with ten times its ulk of a 20% solutionof caustic soda in water until all or nearly all has gone into solution;filter; cool; acidify with hydrochloric acid. From the product of theseoperations tartaric acid, fumaric acid or succinic acid can all berecovered as such by means usual with chemists for such purposes, fromsuch resins inwhose production they have been employed. Maleic acid andmalic acid may be recovered partly as such, but these acids, when usedfor makin our new products, may also be recove entirely or in part onlyas fumaric acid which is a well known transformation product of each ofthose two acids.

.We have described generally a continuous and continuing procedure froma mixture of lycerol and an acid or acids to the fina water-resistantC-stage resin, but we wish it to be understood that either such acontinuous orsuch discontinuous process can be used with equalsatisfaction. That is, we may proceed from the g1 cerol and acids toeither the A-stage or t e Bstage and subse uently to the C-sta or we maybegin wit an A-stage or stage resin and proceed to C-stage resintherefrom.

These resins all belong to the general class of plastics, and while wehave specifically mentioned that they can be used to produce a moldedarticle, it must be obvious to all that they are by no means restrictedto such enumerated uses but can be used in many other places and in manyother operations and for many other purposes where plastic materials canbe used.

We claim:

1. The process of making a resin which comprises heating a mixturecontaining a polynuclear aromatic acid and r. polyhydric alcohol until awater-resistant resin results.

2. A water-resistant resin such as can be obtained from a mixturecontaining a polynuclear aromatic acid and a polyhydric alcohol.

3. The process of making a resin which comprises heating a. mixturecontaining a.

polynuclear aromatic acid and glycerol until a water-resistant resinresults.

4. A water-resistant resin such as can be obtained from a mixturecontainin a polynuclear aromatic acid and glycero.

5. A water-resistant resin such as can be obtained from a polynucleararomatic acid and a polyhydric alcohol.

6. The process of making a resin which comprises heating a polynucleararomatic acid and glycerol until a water-resistant resin results.

7 The process of making a resin'which comprises heating a mixturecontaining diphenic acid and a polyhydric alcohol until awater-resistant resin results. I

8. A water-resistant resin such as can be obtained from a mixturecontaining diphenic acid and a polyhydric alcohol.

CHARLES R. DOWNS. LOUIS WEISBERG.

